Orthometalated N-(Benzophenoxazine)-o-aminophenol: Phenolato versus Phenoxyl States

The molecular and electronic structures of the orthometalated ruthenium(III) and osmium(III) complexes of N-(benzophenoxazine)-o-aminophenol (^OXLH₂) that exhibits versatile redox activities are reported. The redox chemistry of ^OXLH₂ is remarkably different from that of N-(aryl)-o-aminophenol (^APLH₂). The study established that ^OXLH₂ is redox noninnocent and is a precursor of a phenoxyl radical. One of the C-H bonds of ^OXLH₂ is activated by ions, and ^OXLH₂ reveals three different redox states as dianionic phenolato (^OXL^2-), monoanionic phenoxyl radical (^OXL^•-), and zwitterionic phenoxium cation (^OXL^±) states. The reaction of ^OXLH₂ with [Ru^II(PPh₃)₃Cl₂] in boiling toluene in air affords an orthometalated ^OXL^2- complex of ruthenium(III), trans-[(^OXL^2-)Ru^III(PPh₃)₂(Cl)] (1), whereas the similar reaction with [Os^II(PPh₃)₃Br₂] yields an orthometalated ^OXL^•- complex, cis-[(^OXL^•-)Os^III(PPh₃)Br₂] (2). 1 and 2 exhibit ligand-based reversible redox waves due to ^OXL^•-/^OXL^2-, ^OXL^±/^OXL^•-, and M^III/M^II couples. The 1 ⁺ ion is a ^OXL^•- complex of ruthenium(III). 2 ^- exhibits temperature-dependent valence tautomerism due to [Os^II(^OXL^•-) ↔ Os^III(^OXL^2-)] equilibrium. 2 ^2- is a ^OXL^2- complex of osmium(II), while 1 ²⁺ and 2 ⁺ are ^OXL^± complexes of metal(III). 2 is an oxidant and effective catalyst for oxidation of 3,5-di-tert-butylcatechol to the corresponding quinone, and the turnover number is 119.7 h^-1. The UV-vis-NIR absorption spectrum of 1 displays an NIR band at 800 nm due to an intra-ligand-charge-transfer transition, which is absent in 2 incorporating a ^OXL^•- radical. The molecular and electronic structures of 1 and 2 and their oxidized and reduced analogues were confirmed by single-crystal X-ray crystallography, variable-temperature electron paramagnetic resonance spectroscopy, spectroelectrochemical measurements, and density functional theory calculations.